JP2015205463A - Manufacturing method of molded body, manufacturing method of resin pellet, manufacturing method of molded body having plating film, molded body, and resin pellet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide nanoparticles having thermal resistance whose catalytic activity is not deactivated even if the nanoparticles contact high-temperature molten resin, and a manufacturing method thereof.SOLUTION: A manufacturing method of a molded body includes: preparing first solution containing hydrophilic polymer and first solvent; preparing second solution containing metal salt and second solvent; plasticizing and melting first thermoplastic resin into molten resin; creating nanoparticles from the metal salt in the molten resin by adding the first solution and the second solution to the molten resin; and molding the molten resin containing the nanoparticles into a desired shape.

Description

  The present invention relates to a method for producing a molded article containing nanoparticles, a method for producing resin pellets, a method for producing a molded article having a plated film, and further relates to a molded article containing nanoparticles and resin pellets.

  Since monodisperse nanoparticles have specific properties such as the development of fluorescence with a narrow half-value width due to the quantum size effect, their synthesis methods and applications have been studied in recent years. Methods for synthesizing monodisperse nanoparticles are roughly classified into vapor phase methods such as CVD (Chemical Vapor Deposition) and liquid phase methods such as sol-gel method and hydrothermal synthesis method. The vapor phase method has the disadvantages of high production costs and difficulty in obtaining monodispersed fine particles. As the liquid phase method, for example, methods disclosed in Patent Documents 1 to 3 have been reported.

  In Patent Document 1, a metal particle source A, polymer particles B, a substance C that inhibits contact thereof, and a solvent are mixed, and the mixture is subjected to heat treatment and chemical reaction to generate nanoparticle nuclei from the particle source A. Then, a method for producing nanoparticles is disclosed in which heat treatment is performed in a temperature range of 600 ° C. to 1000 ° C. in a region surrounded by polymer particles B. Patent Documents 2 and 3 also disclose a method for synthesizing metal nanoparticles coated with a water-soluble polymer and a water-soluble polymer used therefor.

  Non-Patent Document 1 discloses a continuous reaction method using a high-pressure reaction field as a method for synthesizing metal nanoparticles coated with a water-soluble polymer at high speed. Non-patent document 1 discloses a method for producing platinum, rhodium, palladium, and gold nanoparticles. According to Non-Patent Document 1, in the case of palladium nanoparticles, first, a mixed solvent is prepared from toluene and 1-propanol or acetone. Then, as a raw material, a metal precursor such as palladium acetylacetonato palladium (II) and a water-soluble polymer such as polyvinylpyrrolidone are dissolved in a prepared mixed solvent to obtain a high pressure of 20 MPa, and a temperature atmosphere of 200 ° C. to 300 ° C. Let it pass for tens of seconds. Thereby, metal nanoparticles coated with a water-soluble polymer are continuously synthesized. In Non-Patent Document 1, monodispersed platinum nanoparticles are synthesized, but secondary aggregation is observed in the palladium nanoparticles, and monodispersed palladium nanoparticles are not synthesized.

  On the other hand, an electroless plating method is known as a method for forming a metal film on a resin molded body at low cost. Furthermore, as a method for forming a metal film on a resin molded body without undergoing an etching process, which is a pretreatment for plating, use of a surface modification method of the resin molded body using pressurized carbon dioxide such as supercritical carbon dioxide Proposed. The present inventors have proposed a method in which surface modification treatment using pressurized carbon dioxide is performed simultaneously with injection molding, and metal fine particles such as palladium serving as a catalyst for electroless plating are dispersed on the surface of the resin molded body. (Patent Document 4). According to this method, a plating film can be formed on the surface of the molded body without performing an etching step by performing electroless plating on the resin molded body having palladium unevenly distributed on the surface.

Japanese Patent No. 4767562 JP 2006-239552 A JP 2011-102332 A Japanese Patent No. 4160623

“Synthesis of noble metal ultrafine particles using supercritical fluid”, Yoshifumi Kimura, Masafumi Harada, Rev. High Pressure Sci. Technol, 20 (1), 11-18 (2010)

  However, according to the study by the present inventors, metal fine particles dispersed inside the molded body by a molding method using pressurized carbon dioxide are generated from the resin during molding depending on the type of resin constituting the molded body. It became clear that there is a possibility that the catalytic activity may be deactivated by the volatile gas. For example, when palladium is dispersed in an ABS resin (acrylonitrile / butadiene / styrene copolymer) by the molding method, the resulting molded body may not exhibit a plating reaction. Thus, an experiment was conducted in which the gas generated when the ABS resin was melted was collected and the molded body in which the palladium catalyst was dispersed in the gas atmosphere at room temperature was left, and it was found that the catalytic activity was deactivated.

  This invention solves the said subject, and provides the manufacturing method of the molded object which can be plated containing the nanoparticle which a catalyst activity does not deactivate even if it contacts with high temperature molten resin.

  According to the first aspect of the present invention, there is provided a method for producing a molded body, comprising preparing a first solution containing a hydrophilic polymer and a first solvent, and comprising a metal salt and a second solvent. Preparing a second solution; plasticizing and melting the first thermoplastic resin to form a molten resin; and adding the first solution and the second solution to the molten resin; A method for producing a molded body comprising producing nanoparticles from the metal salt and molding the molten resin containing the nanoparticles into a desired shape is provided.

  In this embodiment, the hydrophilic polymer may be a water-soluble polymer, and the hydrophilic polymer is poly (2-vinylpyridine), poly (3-vinylpyridine), poly (4-vinylpyridine), polyvinyl. It may be at least one selected from the group consisting of pyrrolidone, poly (N-vinylacetamide), poly (vinylamine), and polyvinyl alcohol. The first solvent may be a polar solvent or an alcohol, and the alcohol is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl. It may be at least one selected from the group consisting of -1-propanol. The second solvent may be pressurized carbon dioxide or liquid carbon dioxide. The metal salt may be a palladium salt. The first thermoplastic resin may be a block copolymer including a hydrophilic segment, and the hydrophilic segment of the block copolymer may be a polyether.

  In this aspect, the first solution and the second solution are continuously added to the molten resin to form a mixture, and the first solution and the second solution are continuously added to the first pressure of 3 to 40 MPa while the first solution and the second solution are continuously added. You may adjust to the pressure of. Further, the method includes adjusting the pressure of the first solution and the second solution to a second pressure higher than the first pressure, and adding the first solution and the second solution adjusted to the second pressure to the molten resin. May be. Further, the mixture may be adjusted to a pressure lower than the first pressure, and the first solvent and the second solvent may be separated from the mixture.

According to the second aspect of the present invention, there is provided a method for producing resin pellets, wherein the first molded body is manufactured by the manufacturing method of the first aspect, and the first molded body is cut. A method for producing resin pellets is provided.

  According to a third aspect of the present invention, there is provided a method for producing a molded body, wherein the resin pellet is produced by the method for producing a resin pellet of the third aspect, and the resin pellet and the second thermoplastic resin. And a second molded body containing the nanoparticles is used to provide a method for producing a molded body.

The second thermoplastic resin may be an ABS resin, may not contain the nanoparticles, and may not contain a block copolymer containing a hydrophilic segment.

According to a fourth aspect of the present invention, there is provided a method for producing a molded body having a plating film, wherein the second molded body is produced by the method for producing a molded body according to the third aspect, and the second molding is performed. There is provided a method of manufacturing a molded body having a plating film including forming an electroless plating film on the surface of the body.

  According to a fifth aspect of the present invention, there is provided a molded body comprising a thermoplastic resin, a hydrophilic polymer, and nanoparticles, wherein the molded body is contained in a matrix made of the thermoplastic resin. There is provided a molded article characterized by having a matrix-domain structure in which the hydrophilic polymer domain containing the nanoparticles is present.

  The nanoparticle may have a particle size of 10 nm or less, or 2 nm or less. The nanoparticles may be metal nanoparticles that function as an electroless plating catalyst, and the metal may be palladium. A ratio of the nanoparticles to the hydrophilic polymer may be 0.1 to 30% by weight.

  According to the 6th aspect of this invention, it is a resin pellet, Comprising: The resin pellet manufactured by cutting the molded object of a 5th aspect is provided.

  The nanoparticles contained in the molded article of the present invention have heat resistance that does not deactivate the catalytic activity even when brought into contact with a high-temperature molten resin, do not aggregate even at high temperatures, and have high dispersibility in the resin. Therefore, the molded product of the present invention has high plating reactivity.

It is a flowchart which shows the manufacturing method of the molded object which has a plating film of embodiment. It is the schematic which shows the manufacturing apparatus of the 1st molded object of embodiment. FIGS. 3A and 3B are enlarged schematic views of the downstream-side seal mechanism of the manufacturing apparatus shown in FIG. Fig.4 (a) is a cross-sectional schematic diagram of a 1st molded object, FIG.4 (b) is the schematic diagram which expanded the area | region C shown to Fig.4 (a). In manufacture of the 1st molded object in Example 1, it is a graph which shows the relationship between the operation time of a manufacturing apparatus, and the pressure of the high-pressure kneading zone of a manufacturing apparatus. FIG. 6A is a TEM photograph of a cross section of the resin pellet produced in Example 1, and FIG. 6B is an enlarged TEM photograph of the region C shown in FIG. It is the schematic which shows the nanoparticle manufacturing apparatus used in the comparative example 1. 4 is a TEM photograph of a cross section of a resin pellet produced in Comparative Example 2.

  In the present embodiment, first, a first molded body including nanoparticles is manufactured. And a 1st molded object is cut | judged and a resin pellet is manufactured, The 2nd molded object containing a nanoparticle is manufactured using this resin pellet and 2nd thermoplastic resin. Further, an electroless plating film is formed on the second molded body.

  In the present specification, the “nanoparticle” means a metal nanoparticle having a particle diameter of 100 nm or less, preferably a metal particle having a size of 10 nm or less. In the present specification, “resin pellet” means a small lump (pellet) so that the resin can be easily processed, and the size and shape vary depending on the use of the pellet. It is a small piece of particle-like or columnar resin of about 5 mm. The nanoparticle-containing resin pellet of this embodiment can be processed into a second molded body by plasticizing and melting and injection molding or extrusion molding.

(1) Manufacturing method of 1st molded object First, according to the flowchart shown in FIG. 1, the manufacturing method of the 1st molded object containing a nanoparticle is demonstrated. In the present embodiment, the first molded body is a string-shaped molded body molded by extrusion molding, and resin pellets can be obtained by cutting the first molded body.

  First, a first solution containing a hydrophilic polymer and a first solvent is prepared (S1). Any hydrophilic polymer can be used, but a water-soluble polymer is preferred. Among these, from the viewpoint of increasing the electroless plating reactivity of the second molded body, poly (2-vinylpyridine), poly (3-vinylpyridine), poly (4-vinylpyridine), polyvinylpyrrolidone, poly (N-- Vinylacetamide), poly (vinylamine) and polyvinyl alcohol are more preferred. As the hydrophilic polymer, one kind of hydrophilic polymer may be used, or two or more kinds of hydrophilic polymers may be mixed and used.

  As the first solvent, any solvent can be used as long as it dissolves the hydrophilic polymer, but a polar solvent is preferable because it is a good solvent for the hydrophilic polymer. For example, methanol, ethanol, 1-propanol, Alcohols such as 2-propanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol; ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone, and cyclohexanone; glycols such as ethylene glycol and propylene glycol; Examples include dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, and water. Among these, the first solvent is methanol, ethanol, 1-propanol, 2-propanol, 1 from the viewpoint of compatibility with the second solvent described later and ease of separation from the thermoplastic resin in the process of producing the molded body. Alcohols such as -butanol, 2-butanol, 2-methyl-1-propanol are preferred. As the first solvent, one type of solvent may be used, or two or more types of solvents may be mixed and used.

  The first solution preferably contains 0.1 to 50% by weight, more preferably 0.5 to 20% by weight, of the hydrophilic polymer. The first solution can be prepared by dissolving the hydrophilic polymer in the first solvent by a general-purpose method.

  Next, a second solution containing a metal salt and a second solvent is prepared (step S2). Any metal salt can be used, but in this embodiment, a metal salt that functions as an electroless plating catalyst, that is, a metal salt having a plating catalyst activity is used. Thereby, an electroless plating film can be formed on the second molded body obtained by the present embodiment without separately applying an electroless plating catalyst. Examples of the metal salt having electroless plating catalytic activity include metal salts such as copper, iron, platinum, ruthenium, silver, nickel, chromium, gold, titanium, and palladium, and palladium salt is particularly preferable. More specifically, hexafluoroacetylacetonato palladium (II), platinum dimethyl (cyclooctadiene), bis (cyclopentadienyl) nickel, bis (acetylacetonate) palladium, ferrocene, and the like, and these metals Since a salt (metal complex) has high solubility in pressurized carbon dioxide, it is particularly preferable when pressurized carbon dioxide is used as the second solvent. As the metal salt, one kind of metal salt may be used, or two or more kinds of metal salts may be mixed and used.

  As the second solvent, any solvent can be used as long as it can dissolve the metal salt, and it can be appropriately selected depending on the kind of the metal salt to be used. Examples of the second solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol, and hydrocarbons such as hexane, cyclohexane, and heptane. , Ketones such as acetone, ethyl methyl ketone, methyl isobutyl ketone and cyclohexanone, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, pressurized carbon dioxide and water can be used. Among these, from the viewpoint of compatibility with the first solvent and ease of separation from the thermoplastic resin in the process of producing the molded body, the second solvent is preferably water, alcohol, or pressurized carbon dioxide. As for, liquid carbon dioxide is preferable. As the second solvent, one type of solvent may be used, or two or more types of solvents may be mixed and used.

  As the pressurized carbon dioxide used as the second solvent, pressurized carbon dioxide in a liquid state, a gas state, or a supercritical state can be used. These pressurized carbon dioxides are harmless to the human body, have excellent diffusibility into the molten resin, can be easily removed from the molten resin, and further function as a plasticizer for the molten resin. The pressure and temperature of the pressurized carbon dioxide are arbitrary, but liquid carbon dioxide or supercritical carbon dioxide is preferably used because of its high density and stability. The temperature of the pressurized carbon dioxide is preferably in the range of 5 ° C to 50 ° C. The lower the temperature of the pressurized carbon dioxide, the higher the density and the higher the solvent effect, which is preferable, but 5 ° C. or higher is preferable from the viewpoint of easy cooling control. Moreover, since there exists a possibility that a density may become low and liquid feeding may become unstable when the temperature of pressurized carbon dioxide becomes high, 50 degreeC or less is preferable from a viewpoint of liquid feeding stably. The pressure of the pressurized carbon dioxide is desirably in the range of 4 to 25 MPa. From the viewpoint of obtaining an appropriate solvent effect because the solvent effect is difficult to be expressed when the pressure is low, 4 MPa or more is preferable, and from the viewpoint of suppressing the cost because the high pressure equipment is costly when the pressure is high. 25 MPa or less is preferable. Note that the pressurized carbon dioxide instantaneously becomes high temperature in the plasticizing cylinder, and the pressure fluctuates. Therefore, the above-mentioned pressurized carbon dioxide state, temperature and pressure are values of the pressurized carbon dioxide state, pressure and temperature in a stable state before being introduced into the plasticizing cylinder. The method for preparing pressurized carbon dioxide is not particularly limited, and any conventionally known method can be used.

  The second solution preferably contains 0.1 to 50% by weight of metal salt, and more preferably 0.5 to 50% by weight. The second solution can be prepared by dissolving the hydrophilic polymer in the second solvent by a general-purpose method.

  Next, the first thermoplastic resin is plasticized and melted to obtain a molten resin (step S3). Arbitrary things can be used as a 1st thermoplastic resin, For example, polyamide, such as a polypropylene, polymethylmethacrylate, nylon, polycarbonate, amorphous polyolefin, polyetherimide, polyethylene terephthalate, polyether ether ketone, ABS type Resins, polyphenylene sulfide, polyamideimide, polylactic acid, polycaprolactone, and the like can be used. As the first thermoplastic resin, one kind of thermoplastic resin may be used, or two or more kinds of thermoplastic resins may be mixed and used. Further, the first thermoplastic resin preferably contains a block copolymer containing a hydrophilic segment (hereinafter referred to as “block copolymer” as appropriate). The block copolymer containing a hydrophilic segment tends to move to bleed out to the surface of the molded body with nanoparticles in the second molded body. Thereby, the surface of the second molded body is hydrophilized, the amount of nanoparticles near the surface of the second molded body is increased, and the electroless plating reactivity of the second molded body can be increased.

  The block copolymer containing a hydrophilic segment used in the present embodiment has a hydrophilic segment, and further has another segment different from the hydrophilic segment (hereinafter referred to as “other segment” as appropriate). An anionic segment, a cationic segment, and a nonionic segment can be used for the hydrophilic segment. Examples of the anionic segment include polystyrene sulfonic acid series, the cationic segment includes quaternary ammonium base-containing acrylate polymer series, and the nonionic segment includes polyether ester amide series, polyethylene oxide-epichlorohydrin series, and polyether ester series. It is done. Since it is easy to ensure the heat resistance of a molded object, it is preferable that a hydrophilic segment is a nonionic segment which has a polyether structure. Examples of the polyether structure include oxyethylene groups having 2 to 4 carbon atoms of alkylene, such as oxyethylene groups, oxypropylene groups, oxytrimethylene groups, and oxytetramethylene groups, polyether diols, and polyethers. Diamines, modified products thereof, and polyether-containing hydrophilic polymers are included, and polyethylene oxide is particularly preferable.

  The other segment of the block copolymer is optional as long as it is more hydrophobic than the hydrophilic segment. For example, nylon, polyolefin and the like can be used.

  Commercially available products may be used as the block copolymer, and for example, Pelestat (registered trademark), Peletron (registered trademark) manufactured by Sanyo Chemical Industries, Ltd. may be used. For example, Pelestat 300, NC6321, 1251 manufactured by Sanyo Chemical Industries, Ltd. is a block copolymer obtained by copolymerizing a hydrophilic segment polyether and another segment nylon with an ester bond.

  The first thermoplastic resin can be plasticized and melted by any method. In the present embodiment, the first thermoplastic resin is plasticized and melted in the plasticizing cylinder 210 of the extrusion molding machine 200 shown in FIG.

  Next, by adding the first solution and the second solution to the molten resin, nanoparticles are generated from the metal salt in the molten resin (step S4). The method of adding the first solution and the second solution to the molten resin is arbitrary, but in this embodiment, the first solution and the second solution are supplied into the plasticizing cylinder 210 shown in FIG. In 210, a 1st solution and a 2nd solution are mixed with molten resin. The method of supplying the first solution and the second solution to the plasticizing cylinder is arbitrary. For example, the first solution and the second solution may be mixed and introduced, or may be introduced separately. Further, the first solution and the second solution may be introduced intermittently or continuously. In the present embodiment, the first solution and the second solution are supplied to the plasticizing cylinder 210 using the syringe pumps 11, 12, 31, 32 of the first solution supply mechanism 100 and the second solution supply mechanism 300 shown in FIG. Supply continuously. In the present embodiment, the molten resin, the first solution, and the second solution are continuously mixed in the plasticizing cylinder 210 to form a mixture, and metal nanoparticles are continuously generated in the mixture.

  The mechanism by which nanoparticles are formed in the mixture is assumed as follows. In the high-temperature molten resin, the metal salt metal is thermally reduced to form metal particles. At this time, the generated metal particles are presumed to have higher affinity with the hydrophilic polymer than the molten resin. For this reason, the metal fine particles do not exist in the thermoplastic resin but exist in the hydrophilic polymer domain. Since metal particles are generated in the presence of such a hydrophilic polymer, aggregation of the generated metal particles is suppressed, and it is estimated that nanoparticles having a particle diameter of 100 nm or less are generated. In addition, when alcohol is used as the first solvent, it is presumed that the metal salt is alcohol reduced also by the first solvent.

  The temperature of the mixture of the first thermoplastic resin, the first solution, and the second solution, that is, the temperature at which the nanoparticles are generated can be appropriately set according to the type of the first thermoplastic resin. However, from the viewpoint of producing nanoparticles, the temperature is preferably 150 to 400 ° C, more preferably 200 to 350 ° C.

  The pressure of the mixture of the first thermoplastic resin, the first solution, and the second solution, that is, the pressure at which the nanoparticles are generated is preferably adjusted to 3 to 40 MPa. When the pressure of the mixture is 3 MPa or more, the dispersibility of the nanoparticles in the molten resin becomes good. Moreover, the burden to the apparatus containing a screw, a motor, etc. is reduced as the pressure of a mixture is 40 Mpa or less. When the first solution and the second solution are introduced, the viscosity and pressure of the molten resin are lowered. Therefore, it is preferable to adjust the pressure of the molten resin before the first solution and the second solution molten resin are mixed to 5 MPa or more.

  While the molten resin, the first solution, and the second solution are continuously mixed, the pressure of the mixture may vary as long as it is within the range of the first pressure described above. Is preferably controlled within a range of ± 2 MPa, more preferably within a range of ± 1 MPa. The first solvent and the second solvent may not be in a supercritical state when kneaded with the molten resin in the plasticizing cylinder. A supercritical fluid has a small change in density due to a change in pressure, whereas a fluid that has not reached the supercritical state has a large change in density due to a change in pressure. For this reason, there is a possibility that the density rapidly decreases due to a slight change in pressure, vaporizes, and the metal fine particles aggregate. In the present embodiment, even when the first solvent or the second solvent that is not in the supercritical state is used, that is, the first solvent or the second solvent in which the density change accompanying the pressure change is large and the solvent performance is difficult to maintain. Even in the case of using a solvent, a good dispersion state of the nanoparticles can be maintained by maintaining the pressure of the mixture at a high pressure (first pressure).

  Although the method of maintaining the pressure of the mixture at the first pressure is arbitrary, in this embodiment, the pressure of the mixture is maintained at the first pressure by providing a sealing mechanism in the plasticizing cylinder. The sealing mechanism provided in the present embodiment is a mechanism that does not allow a mixture having a pressure less than a predetermined pressure to flow downstream of the sealing mechanism. With this sealing mechanism, the pressure of the mixture on the upstream side of the sealing mechanism can be increased and adjusted to a desired pressure (first pressure). As shown in FIG. 3, the seal mechanism used in the present embodiment is a seal mechanism including a seal ring provided on the outer peripheral surface of the screw via a spring. The details of the sealing mechanism shown in FIG. 3 will be described in Example 1 described later.

  The pressure of the first solution and the second solution mixed with the molten resin is preferably adjusted to a second pressure higher than the first pressure, for example, preferably 5 to 40 MPa. By making the pressure of the first solution and the second solution higher than that of the molten resin, the introduction of the first solution and the second solution into the plasticizing cylinder can be facilitated.

  In the mixing step of the molten resin, the first solution, and the second solution, the mixing ratio of the molten resin, the first solution, and the second solution is the content of the hydrophilic polymer in the first solution, the metal in the second solution The content can be appropriately determined in consideration of the content of salt, the content of nanoparticles in the produced molded article, and the like. For example, the molten resin, the first solution, and the second solution may be mixed so that the content of the nanoparticles in the produced molded body is preferably 0.001 to 2% by weight. . Further, the ratio of the metal in the metal salt to the hydrophilic polymer is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and the first solution and the second solution May be mixed.

  In the present embodiment, the pressure of the mixture of the molten resin, the first solution, and the second solution, that is, the pressure of the molten resin containing the generated nanoparticles is further adjusted to a pressure lower than the first pressure. Thus, it is preferable to separate the first solvent and the second solvent from the molten resin. By depressurizing the mixture, the first solvent and the second solvent contained in the mixture can be gasified and separated. The pressure reduction of the mixture can be performed by any method. For example, the screw provided in the plasticizing cylinder may be provided with a portion having a small diameter and a deep flight. In addition, a vent that communicates with the outside may be provided in the plasticizing screw, and the inside of the plasticizing cylinder may be opened to the atmosphere, or the inside of the plasticizing cylinder may be reduced to a pressure lower than the atmospheric pressure by a vacuum pump.

  Next, the molten resin containing nanoparticles is formed into a desired shape (step S5). In the present embodiment, the molten resin is extruded from the die 29 provided at the tip of the plasticizing screw 210 shown in FIG. 2 to obtain a string-like molded body.

(2) Structure of first molded body The first molded body manufactured in the present embodiment includes a first thermoplastic resin, a hydrophilic polymer, and nanoparticles. As shown in FIG. 4A, the first molded body has a matrix (sea) 2 in which a hydrophilic polymer domain (island) 2 exists in a matrix (sea) 1 made of the first thermoplastic resin. -It has a domain structure (sea-island structure). And as shown in FIG.4 (b), the nanoparticle 3 exists in the domain (island) 2 of a hydrophilic polymer. Most of the nanoparticles 3 exist in the domain (island) 2 of the hydrophilic polymer, and few nanoparticles 3 exist in the matrix (sea) 1 made of the first thermoplastic resin. Since the first molded body has such a structure, nanoparticles are generated in the presence of the hydrophilic polymer. Therefore, it is presumed that the nanoparticles are prevented from agglomerating and become fine particles. Usually, a plurality of nanoparticles 3 are generated in one domain (island) 2, but one nanoparticle 3 may be generated in one domain (island) 2. Moreover, in the manufacturing process of the 2nd molded object mentioned later, the structure by which a nanoparticle is coat | covered with a hydrophilic polymer is maintained, Thereby, even when volatile gas generate | occur | produces from a 2nd thermoplastic resin, a nanoparticle Is presumed not to deactivate the catalytic activity.

  The nanoparticles contained in the first molded body have a particle size of 100 nm or less, preferably 10 nm or less, more preferably 2 nm or less. If the particle diameter of the nanoparticles is 100 nm or less, the dispersibility in the resin is good, and it can be expected that the molded product containing the nanoparticles of the present embodiment has higher functionality. Furthermore, if the particle diameter of the nanoparticles is 10 nm or less, the dispersibility in the resin is further improved. Moreover, when the segregation property to the surface of a molded object increases and a nanoparticle functions as an electroless plating catalyst, a plating reaction is accelerated | stimulated. According to the study by the present inventors, when the first molded body is cut into resin pellets, and the second molded body is molded from the resin pellets and the second thermoplastic resin by injection molding, the particle diameter is It has been found that single nano-order nanoparticles of 10 nm or less are easy to concentrate on the surface of the molded body. In addition, the particle diameter of the nanoparticle in this specification is the value measured in the TEM photograph of a nanoparticle. However, when the particle diameter is 1 nm or less, the particle diameter is below the measurement limit of TEM, and the particle diameter may not be confirmed by a TEM photograph. In this case, the particle diameter of the nanoparticles is 1 nm or less. For example, as shown in a TEM photograph in Example 1 described later shown in FIG. 6, the hydrophilic polymer domain (island) 2 has a large number of nanoparticles having a particle diameter of 1 nm or less which is less than the measurement limit of TEM. Can be estimated from the contrast of the TEM photograph.

  The nanoparticles contained in the first molded body of the present embodiment are produced (synthesized) in a production method different from the present embodiment, for example, in a production field (synthesis field) other than in the molten resin, and thereafter The particle diameter is smaller than the nanoparticles contained in the molded body produced by the production method in which the nanoparticles are taken out from the production field (synthesis field) and mixed with the molten resin. The reason for this is not clear, but for example, there is a risk of aggregation of the nanoparticles if a process for taking out the synthesized (synthesized) nanoparticles from the production field (synthesis field) is provided. The reason is that the metal particles are easily atomized because the metal salt is reduced at a high speed.

  The content of the nanoparticles in the first molded body is preferably 0.001 to 2% by weight. If the content of the nanoparticles in the first molded body is within this range, the electroless plating film can be efficiently formed on the second molded body produced in the present embodiment. In the first molded body, the ratio of the nanoparticles to the hydrophilic polymer is preferably 0.1 to 30% by weight, and more preferably 0.5 to 20% by weight. When the ratio of the nanoparticles to the hydrophilic polymer is lower than 0.1% by weight, the content of the nanoparticles in the second molded body is lowered, and the plating reactivity may be lowered, or the plating film may be uneven. There is. Further, when the ratio of the nanoparticles to the hydrophilic polymer is more than 30% by weight, when volatile gas is generated from the second thermoplastic resin in the production process of the second molded body, There is a risk that the protection will be insufficient and the nanoparticles will deactivate the catalytic activity.

(3) Manufacture of resin pellets The manufactured string-like molded body (first molded body) containing nanoparticles is cooled by passing through a water tank or the like, and then cut using a general-purpose cutting device such as a strand cutting device. Thus, resin pellets are manufactured (step S6). It is preferable from the viewpoint of productivity of the resin pellets that the first molded body is continuously manufactured, cooled, and cut.

(4) Manufacture of 2nd molded object Next, the 2nd molded object containing the said nanoparticle is manufactured using the 2nd thermoplastic resin with the manufactured resin pellet (step S7).

  In this embodiment, the resin pellet containing nanoparticles is a master batch, and the second thermoplastic resin corresponds to a base resin into which the master batch is blended. In the present specification, the “masterbatch” is a resin pellet containing a high concentration of functional materials such as dyes, pigments and other additives, and is mixed with a base resin not containing the functional material. Molded together. When the master batch is used, the handling of the material is easy and the weighing accuracy is improved as compared with the case where the functional material is directly added to the base resin and molded. Moreover, when a masterbatch is used, it has the advantage that the molded object containing a functional material can be manufactured using a general purpose molding machine. In the present embodiment, the nanoparticles correspond to a functional material contained in the master batch (resin pellet).

  As the second thermoplastic resin, any resin can be used similarly to the first thermoplastic resin, one kind of thermoplastic resin may be used, and two or more kinds of thermoplastic resins are mixed. It may be used. Further, the second thermoplastic resin may contain various inorganic fillers such as glass fiber, talc, and carbon fiber.

  Moreover, since the resin pellet contains nanoparticles that function as an electroless catalyst, the second thermoplastic resin does not need to contain the same nanoparticles, and may not contain nanoparticles from the viewpoint of cost reduction. preferable. Furthermore, from the viewpoint of heat resistance of the second molded body, the second thermoplastic resin preferably does not have a block copolymer including a hydrophilic segment.

  The resin pellets and the second thermoplastic resin can be molded into a desired shape using a general-purpose molding machine such as an injection molding machine or an extrusion molding machine to obtain a second molded body containing nanoparticles.

  In the molding process of the second molded body, the hydrophilic polymer continues to coat the metal particles without being thermally decomposed even in a high temperature atmosphere, so that the nanoparticles do not aggregate. Therefore, even if it contacts with high temperature molten resin, a nanoparticle can be maintained and high dispersibility can be maintained. For this reason, the dispersibility of the nanoparticles in the second molded body is improved, and the segregation on the surface of the molded body is increased due to the fine particles. As a result, the plating reactivity of the second molded body can be improved.

  Furthermore, in this embodiment, when the nanoparticles are kneaded with the molten resin, the hydrophilic polymer coats the metal particles without thermal decomposition, so that the metal particles are protected from the volatile gas generated from the molten resin. The Therefore, even when a resin that generates a volatile gas, such as an ABS resin, is used as the second thermoplastic resin, there is no possibility that the nanoparticles deactivate the catalytic activity when the second molded body is molded.

(5) Electroless plating A plating film is formed on the produced second molded body containing nanoparticles by a general electroless plating method (step S8 in FIG. 1). At this time, the nanoparticles contained in the molded body act as an electroless plating catalyst. Therefore, in this embodiment, an electroless plating film can be formed on the second molded body without separately applying an electroless plating catalyst. In the electroless plating step, the electroless plating pretreatment liquid or the electroless plating liquid comes into contact with the hydrophilic polymer covering the nanoparticles. Thereby, it is presumed that the hydrophilic polymer covering the nanoparticles is removed and does not cover the metal particles, or is swollen and allows the plating solution to penetrate the hydrophilic polymer. As a result, the plating solution and the nanoparticles can be directly contacted, and it is assumed that the plating reaction is accelerated.

  Hereinafter, the present invention will be further described using examples and comparative examples. However, the present invention is not limited to the examples and comparative examples described below.

[Example 1]
In this example, first, a first molded body containing nanoparticles was manufactured using the first solution, the second solution, and the first thermoplastic resin by the manufacturing apparatus 1000 shown in FIG. And the 1st molded object was cut and the resin pellet was manufactured, and the 2nd molded object containing a nanoparticle was manufactured using this resin pellet and the 2nd thermoplastic resin. Furthermore, an electroless plating film was formed on the second molded body.

  In this example, polyvinyl pyrrolidone (made by ISP, PVP K-30, molecular weight 40000) (hereinafter referred to as “PVP” as appropriate) is used as the hydrophilic polymer, and ethanol is used as the first solvent to prepare the first solution. A second solution was prepared using hexafluoroacetylacetonato palladium (II) (hereinafter referred to as “palladium complex” as appropriate) as the metal salt and liquid carbon dioxide as the second solvent. As the first thermoplastic resin, a block copolymer containing a hydrophilic segment (manufactured by Sanyo Kasei, Pelestat PL1251) is used. Resin and polyamide (PA) alloy resin (Toyolac SX01, manufactured by Toray) was used.

(1) Manufacturing apparatus for first molded body First, a manufacturing apparatus 1000 used for manufacturing the first molded body in this embodiment will be described. As shown in FIG. 2, the manufacturing apparatus 1000 includes an extrusion molding machine 200 having a plasticizing cylinder 210, a first solution supply mechanism 100 that supplies a first solution to the plasticizing cylinder 210, and a second solution that is a plasticizing cylinder. 2nd solution supply mechanism 300 supplied to 210, and a control device (not shown) are provided. The control device controls operations of the extrusion molding machine 200, the first solution supply mechanism 100, and the second solution supply mechanism 300.

(A) Extruder Machine The extruder 200 shown in FIG. 2 includes a plasticizing cylinder 210, a die 29 provided at the tip of the plasticizing cylinder 210, and a screw 20 that is rotatably disposed in the plasticizing cylinder 210. A screw drive mechanism 27 for driving the screw 20, an upstream side seal mechanism S <b> 1 and a downstream side seal mechanism S <b> 2 disposed in the plasticizing cylinder 210, and a vacuum pump P connected to the plasticizing cylinder 210. In the present embodiment, in the plasticizing cylinder 210, the plasticized and melted molten resin flows from the right hand to the left hand in FIG. Therefore, in the plasticizing cylinder 210 of this embodiment, the right hand in FIG. 2 is defined as “upstream” or “rear”, and the left hand is defined as “downstream” or “front”. Note that the extruder 200 of the present embodiment, like the configuration of a conventionally known extruder, rotates the screw 20 counterclockwise when viewed from the rear side of the plasticizing cylinder 210. It is configured to perform forward rotation sent forward (nozzle side) and reverse rotation when rotated clockwise.

  On the upper side surface of the plasticizing cylinder 210, in order from the upstream side, a resin supply port 201 for supplying a thermoplastic resin to the plasticizing cylinder 210, and a first and second solution for introducing the first and second solutions into the plasticizing cylinder 210. A vent 203 is formed to exhaust the first and second solvents gasified from the introduction port 202 and, if necessary, from the plasticizing cylinder 210. The resin supply port 201 and the introduction port 202 are provided with a resin supply hopper 211 and an introduction valve 212, respectively, and a vacuum pump P is connected to the vent 203. The introduction valve 212 is connected to the first and second solution supply mechanisms 100 and 300 provided outside the extrusion molding machine 200.

  A band heater 220 is disposed on the outer wall surface of the plasticizing cylinder 210, whereby the plasticizing cylinder 210 is heated and the thermoplastic resin is plasticized. Further, a sensor (not shown) for monitoring pressure and temperature is provided at a position facing the inlet 202 on the lower side surface of the plasticizing cylinder 210 and a position facing the vent 203, respectively.

  In the extruder 200 having such a structure, thermoplastic resin is supplied from the resin supply port 201 into the plasticizing cylinder 210, and the thermoplastic resin is plasticized by the band heater 220 to become molten resin, so that the screw 20 rotates in the forward direction. Is sent downstream. The molten resin sent to the vicinity of the introduction port 202 is contact-kneaded with the introduced first and second solutions under high pressure. Next, by reducing the internal pressure of the molten resin that has been contact-kneaded with the first and second solutions, the gasified first and second solvents are separated from the molten resin and exhausted from the vent 203. Then, the molten resin sent further forward is pushed out from the die 29. As a result, in the plasticizing cylinder 210, the plasticizing zone 21 that plasticizes the thermoplastic resin into the molten resin in order from the upstream side, the molten resin, and the first and second solutions introduced from the inlet 202 are pressurized. The first and second solvents separated from the molten resin are exhausted from the vent 203 by lowering the internal pressure of the high-pressure kneading zone 22 for contact-kneading and the molten resin contact-kneaded with the first and second solutions. A decompression zone 23 is formed. Further, a replasticization zone 24 is provided downstream of the decompression zone 23. In order to efficiently perform the kneading of the molten resin with the first and second solutions, the plasticizing cylinder 210 is provided with a plurality of inlets 202 and vents 203, and the plasticizing cylinder 210 has a high-pressure kneading zone 22 and a reduced pressure. A plurality of zones 23 may be formed.

  An upstream seal mechanism S1 and a downstream seal mechanism S2 are disposed between the plasticizing zone 21, the high-pressure kneading zone 22, and the decompression zone 23, respectively. As the upstream seal mechanism S1, any seal mechanism can be used as long as the backflow of the resin to the upstream side can be suppressed. In this embodiment, a seal ring used for conventional foam molding or the like is employed. The downstream side seal mechanism S2 is arranged on the downstream side of the downstream side seal mechanism S2 in a state where the pressure of the molten resin is adjusted to the first pressure of 3 MPa to 40 MPa in the high pressure kneading zone 22 upstream of the downstream side seal mechanism S2. A sealing mechanism capable of flowing the molten resin to the decompression zone 23 is used. In the present embodiment, a seal mechanism including a seal ring 60 provided on the outer peripheral surface of the screw 20 via a spring shown in FIG. 3 is used as the downstream seal mechanism S2. The detailed structure and function of the downstream side seal mechanism S2 will be described later.

(B) First Solution Supply Mechanism and Second Solution Supply Mechanism Next, the first solution supply mechanism 100 and the second solution supply mechanism 300 shown in FIG. 2 will be described. The first solution supply mechanism 100 and the second solution supply mechanism 300 are connected to the introduction valve 212 of the extrusion molding machine 200 via the back pressure valve 250, and supply the first solution and the second solution to the molding machine 200, respectively. To do. The first solution supply mechanism 100 can suck the first solution from the first solution storage container 10 for storing the first solution and the first solution, then increase the pressure to a predetermined pressure, and further feed the liquid at a constant flow rate. The two syringe pumps 11 and 12, two automatic air valves for suction 13 and 14 arranged in the pipe, and two automatic air valves for liquid feeding 15 and 16 are configured.

  The second solution supply mechanism 300 includes a carbon dioxide cylinder 37, a storage tank 30 connected to the carbon dioxide cylinder 37 via the Coriolis flow meter 38 and the metal salt dissolution tank 39, and the amount of liquid carbon dioxide in the storage tank 30. A differential pressure type liquid level gauge 40 to be monitored, two syringe pumps 31 and 32 connected to the storage tank 30 via a valve 41, two suction air automatic valves 33 and 34 arranged in a pipe, and two liquids It consists of air sending automatic valves 35 and 36. The second solution is prepared in the storage tank 30, sucked from the storage tank 30 by the two syringe pumps 31, 32, pressurized to a predetermined pressure, and further fed to the extruder 200 at a constant flow rate.

  In the second solution supply mechanism 300, the carbon dioxide cylinder 37 includes a heater (not shown), pressurizes the carbon dioxide in the cylinder by heating with the heater, and supplies the carbon dioxide to the storage tank 30. The amount of carbon dioxide supplied to the storage tank 30 is monitored by a Coriolis flow meter 38, and when a predetermined amount of carbon dioxide is supplied to the storage tank 30, an automatic valve (not shown) is closed to the carbon dioxide storage tank 30. Stop supplying.

  The storage tank 30 includes a heater for heating and a heat exchanger connected to a chiller as a temperature control mechanism (not shown), and the carbon dioxide in the storage tank 30 is maintained by maintaining the storage tank 30 at a predetermined temperature. Is kept in a vapor-liquid equilibrium state, and the density of liquid carbon dioxide is kept constant. In the storage tank 30, the liquid phase of carbon dioxide is heated by a heater provided in the lower part of the storage tank 30, and the gas phase is cooled by a heat exchanger provided in the upper part of the storage tank 30. The amount of liquid carbon dioxide is monitored by a differential pressure type level gauge 40.

  In the second solution supply mechanism 300, a metal salt is introduced into the metal salt dissolution tank 39 and carbon dioxide is supplied from the carbon dioxide cylinder 37 via the metal salt dissolution tank 39 to the storage tank 30. In the metal salt dissolution tank 39, the metal salt is dissolved in carbon dioxide and flows into the storage tank 30 as it is. Thereby, the second solution is prepared in the storage tank 30. The volume of the storage tank 30 used in this example was 40L.

  Since the first solution supply mechanism 100 and the second solution supply mechanism 300 have syringe pumps 11, 12, 31, and 32 capable of controlling the flow rate and pressure, the first and second flow rates and pressures controlled to a predetermined amount. The solution can be sent to the extruder 200. The syringe pumps 11, 12, 31, and 32 open the suction air automatic valves 13, 14, 33, and 34, suck the solution into the syringe pump, and then close and pressurize the valve to keep it at a predetermined pressure. . When liquid is fed, the liquid automatic air valves 15, 16, 35, and 36 are opened, and liquid can be fed at a constant flow rate by pushing the syringe of the syringe pump at a constant speed. The pressure (second pressure) of the first solution and the second solution introduced into the plasticizing cylinder 210 of the extruder 200 is adjusted by the set pressure of the back pressure valve 250. In this embodiment, the first solution and the second solution are mixed before the back pressure valve 250 (upstream side) and introduced into the plasticizing cylinder 210 as a mixed solution.

  In each of the first solution supply mechanism 100 and the second solution supply mechanism 300, when one pump (for example, syringe pumps 11 and 31) is feeding liquid, the other pump (syringe pumps 12 and 32) supplies the solution. Wait for suction and pressurization. When the pressurized solution in one of the pumps (syringe pumps 11 and 31) being pumped becomes empty, the pump is switched, and this time, the other pumps (syringe pumps 12 and 32) are used to feed the liquid. Start. As a result, the pressure and flow rate can be kept constant, and the first and second solutions can be fed (supplied) from the first solution supply mechanism 100 and the second solution supply mechanism 300 to the extrusion molding machine 200. The extrusion molding machine 200 can continuously mold the first molded body containing nanoparticles.

(C) Downstream side sealing mechanism The downstream side sealing mechanism S2 provided in the extrusion molding machine 200 will be described. In the present embodiment, as the downstream seal mechanism S2, a seal mechanism including a seal ring 60 provided on the outer peripheral surface of the screw 20 via a spring described below is used.

  As shown in FIG. 2, the screw 20 of this embodiment has a reduced diameter portion 50 that is reduced in diameter in the boundary region between the high-pressure kneading zone 22 and the decompression zone 23 as compared with the region adjacent to the boundary region. (See FIG. 3). The downstream seal ring 60 is externally fitted to the reduced diameter portion 50 so as to be movable in the axial direction (front-rear direction) within the range of the reduced diameter portion 50. The reduced diameter portion 50 and the downstream seal ring 60 constitute a downstream seal mechanism S2.

  In the screw 20, a downstream screw portion 51 located in the decompression zone 23 is provided adjacent to the downstream side of the reduced diameter portion 50, and the downstream screw portion 51 has a diameter larger than that of the reduced diameter portion 50, and thus the reduced diameter. It has an end surface 51 a continuous with the portion 50. Four holes 51b are formed in the end surface 51a, and a spring piston 61 is disposed in each hole 51b. The spring piston 61 includes a plurality of disc springs 63 disposed in the hole 51b, a ring 64 disposed in contact with the disc spring 63 in the hole 51b, and a part protruding from the hole 51b, A disc spring 63 and a shaft 62 penetrating the ring 64 are formed. As shown in FIG. 3A, the ring 64 of the spring piston 61 is in contact with the downstream seal ring 60, and the downstream seal ring 60 is in the upstream direction (the direction indicated by the arrow in FIG. 3A). Energized. As a result, the inner wall 60a of the seal ring 60 and the outer peripheral surface 50a of the reduced diameter portion 50 come into contact with each other, and communication between the high pressure kneading zone 22 and the decompression zone 23 is blocked.

  Next, the operation of the downstream seal mechanism S2 will be described. As the screw 20 rotates forward, the molten resin flows from upstream to downstream. As a result, the molten resin staying in the high-pressure kneading zone 22 pushes the downstream seal ring 60 in the downstream direction. However, as shown in FIG. 3 (a), the downstream seal ring 60 is urged in the upstream direction by the spring piston 61, and the communication between the high-pressure kneading zone 22 and the decompression zone 23 is cut off. It cannot flow from the kneading zone 22 to the decompression zone 23.

  Further, when the screw 20 rotates in the forward direction, the molten resin continues to flow from the plasticizing zone 21 to the high pressure kneading zone 22 while the communication between the high pressure kneading zone 22 and the decompression zone 23 is blocked. Pressure increases. When the pressure in the high-pressure kneading zone 22 becomes equal to or higher than a predetermined pressure, the downstream seal ring 60 is pushed by the molten resin in the downstream direction and starts to move. 3B, the inner wall 60a of the downstream seal ring 60 and the outer peripheral surface 50a of the reduced diameter portion 50 are separated from each other, the gap G is opened, and the molten resin is pressurized through the gap G. It becomes possible to move from the kneading zone 22 to the decompression zone 23.

  The downstream seal mechanism S2 increases the pressure of the molten resin (in this embodiment, a mixture of the molten resin, the first solution, and the second solution) in the high-pressure kneading zone 22 upstream of the downstream seal mechanism S2. It can be maintained at a high pressure (first pressure) with little pressure fluctuation. Hereinafter, a method for adjusting the pressure of the molten resin using the downstream-side seal mechanism S2 will be described. First, the screw 20 is rotated forward in a state where the communication between the high-pressure kneading zone 22 and the decompression zone 23 is blocked by the downstream seal mechanism S2. Since the upstream side seal mechanism S1 suppresses the back flow from the high pressure kneading zone 22 to the plasticizing zone 21, the molten resin continues to flow from the plasticizing zone 21 to the high pressure kneading zone 22, and the pressure in the high pressure kneading zone 22 increases. To do. When the pressure of the molten resin in the high-pressure kneading zone 22 is further increased to a predetermined pressure or higher by rotating the screw in the forward direction, the high-pressure kneading zone 22 and the decompression zone 23 are communicated with each other by the downstream seal mechanism S2. The resin flows to the downstream decompression zone 23. When the molten resin flows to the downstream decompression zone 23, the pressure in the high-pressure kneading zone 22 begins to decrease, and when the pressure in the high-pressure kneading zone 22 falls below a predetermined pressure, the downstream-side seal mechanism S2 again causes the high-pressure kneading zone 22 Communication between 22 and the decompression zone 23 is blocked. Since the screw rotates in the forward direction, the pressure in the high-pressure kneading zone 22 rises again, and when the pressure exceeds a predetermined pressure, the high-pressure kneading zone 22 and the decompression zone 23 communicate with each other again by the downstream seal mechanism S2, and the molten resin Flows to the downstream decompression zone 23. As described above, the downstream seal mechanism S2 repeats communication and blocking between the high-pressure kneading zone 22 and the decompression zone 23 in accordance with the pressure in the high-pressure kneading zone 22. As a result, the pressure of the molten resin in the high-pressure kneading zone 22 can be maintained at a high pressure (first pressure) with little pressure fluctuation.

(2) Manufacture of the 1st molded object The 1st molded object was manufactured using the manufacturing apparatus 1000 shown in FIG. 2 demonstrated above.

(A) Preparation of first solution and second solution To 46.3 g of PVP (hydrophilic polymer), 600 g of ethanol (first solvent) was added and stirred for complete dissolution. Ethanol was further added to this solution to make the total volume 1L. Thereby, the 1st solution A whose PVP density | concentration in a solution is 46.3 g / L was prepared. The prepared first solution A was placed in the first solution storage container 10 of the first solution supply mechanism 100.

  Next, the second solution was prepared in the second solution supply mechanism 300. First, the carbon dioxide cylinder 37 was heated to 35 ° C. by a heater (not shown), the pressure of carbon dioxide was increased to 9 MPa, and 10 kg of carbon dioxide was supplied to the storage tank 30.

  The carbon dioxide in the storage tank 30 was controlled to a gas-liquid mixed state of 20 ° C. and 5.7 MPa by a temperature control mechanism (not shown). Specifically, the liquid phase of carbon dioxide was heated by a heater (not shown) adjusted to 20 ° C., and the gas phase of carbon dioxide was cooled by a heat exchanger (not shown) connected to a 10 ° C. chiller. When the pressure of carbon dioxide rises from 5.7 MPa to 0.1 MPa, in an unillustrated heat exchanger, an automatic solenoid valve opens and the cooling water of the chiller flows into the heat exchanger to cool the gas phase, thereby reducing the pressure of carbon dioxide. Lowered. On the other hand, when the pressure of carbon dioxide decreased from 5.7 MPa to 0.1 MPa, the flow of cooling water into the heat exchanger was stopped. As a result, the pressure of carbon dioxide in the storage tank 30 was controlled to 5.7 ± 0.1 MPa. In the present example in which 10 kg of carbon dioxide was supplied to the empty storage tank 30, the amount of carbon dioxide to be vaporized was large, so the liquid carbon dioxide in the storage tank 30 was 3 kg.

  Next, 110 g of palladium complex (metal salt) was placed in the metal salt dissolution tank 39 of the second solution supply mechanism 300. Then, 6 kg of carbon dioxide was resupplied from the carbon dioxide cylinder 37 to the storage tank 30 through the metal salt dissolution tank 39 in which the palladium complex was arranged. As a result, the palladium complex disposed in the metal salt dissolution tank 39 is dissolved in carbon dioxide and supplied to the storage tank 30 together with carbon dioxide. In the storage tank 30, the palladium complex (metal salt) and liquid carbon dioxide ( A second solution B consisting of the second solvent) was prepared. The carbon dioxide in the storage tank 30 was controlled to a gas-liquid mixed state of 20 ° C. and 5.7 MPa, and the liquid carbon dioxide was 11 kg and 14.2 L in the total amount of carbon dioxide of 16 kg. Therefore, in the second solution in the storage tank 30, the concentration of the palladium complex with respect to the liquid carbon dioxide was 1% by weight (7.7 g / L).

(B) Production of first molded body The first solution A and the second solution B were pressurized to 15 MPa. In the first solution supply mechanism 100, the first solution A in the first solution storage container 10 was sucked by the syringe pump 11 and then pressurized to 15 MPa. In the second solution supply mechanism 300, the syringe pumps 31 and 32 were first cooled to 10 ° C. in order to suppress vaporization of liquid carbon dioxide. Next, the valve 41 was opened, the second solution B was sucked by the syringe pump 31, and then the pressure was increased to 15 MPa. Thereby, the density of the liquid carbon dioxide and the dissolution concentration of the palladium complex increased by about 23%, and the concentration of the palladium complex with respect to the liquid carbon dioxide in the second solution was 9.6 g / L.

  After boosting the first solution A and the second solution B, the syringe pumps 11 and 31 were switched to flow control, and the first solution A and the second solution B were fed to the plasticizing cylinder 210. The first solution and the second solution were mixed before the back pressure valve 250 (upstream side) to form a mixed solution. The pressure for introducing the mixed solution into the plasticizing cylinder 210 was adjusted to 15 MPa (second pressure) by the back pressure valve 250. Thereby, the inside of the system up to the introduction valve 212 for introducing the fluid into the plasticizing cylinder 210 was pressurized with the mixed solution.

  Next, in the extrusion molding machine 200, the plasticizing zone 21 was adjusted to 190 ° C., the high-pressure kneading zone 22 to 120 ° C., the decompression zone 23 to 170 ° C., and the re-plasticizing zone 24 to 170 ° C. by the band heater 220. In the extrusion molding machine 200, the first thermoplastic resin was supplied from the resin supply hopper 211, and the screw 20 was rotated forward. Thus, the thermoplastic resin was heated and kneaded to obtain a molten resin. By rotating the screw 20 forward, the molten resin was caused to flow from the plasticizing zone 21 to the high-pressure kneading zone 22. In the high-pressure kneading zone 22 in which the upstream side sealing mechanism S1 is provided on the upstream side and the downstream side sealing mechanism S2 is provided on the downstream side, the pressure of the molten resin before the mixed fluid was introduced was adjusted to 14 ± 1 MPa.

  Next, the introduction valve 212 was opened, and the mixed solution of the first solution and the second solution was introduced into the high-pressure kneading zone 22 at a constant flow rate by the syringe pumps 11 and 31. The flow rate of the first solution was 12 mL / min, and the flow rate of the second solution was 8.7 mL / min. In the first solution supply mechanism 100, the first solution was continuously supplied to the plasticizing cylinder 210 by alternately feeding liquid using the syringe pump 11 and the syringe pump 12. Similarly, in the first solution supply mechanism 300, the second solution is continuously supplied to the plasticizing cylinder 210 by alternately feeding liquid using the syringe pump 31 and the syringe pump 32. In the storage tank 30, as the amount of the second solution B decreases, a part of the liquid carbon dioxide is gasified to increase the palladium complex concentration in order to maintain the vapor-liquid equilibrium state of carbon dioxide. For this reason, according to consumption of the 2nd solution B, the carbon dioxide was automatically replenished to the storage tank 30 from the carbon dioxide cylinder 37 regularly, and the density | concentration of the palladium complex in the 2nd solution B was stabilized.

  By rotating the screw 20 forward, the mixed solution was mixed with the molten resin in the high-pressure kneading zone 22 to obtain a mixture. As shown in FIG. 5, the pressure inside the plasticizing cylinder 210 monitored by a pressure sensor (not shown) provided immediately below the introduction valve 212 is stable at 9.0 ± 1.5 MPa as shown in FIG. there were. That is, in this embodiment, in the high-pressure kneading zone 22, the molten resin, the first solution, and the second solution are continuously mixed, and during the continuous mixing, the molten resin, the first solution, and the first solution are mixed. The pressure of the mixture with the two solutions was adjusted to a first pressure of 9.0 ± 1.5 MPa to produce nanoparticles in the molten resin.

  Further, by rotating the screw 20 in the forward direction, the molten resin was caused to flow into the decompression zone 23 while the high-pressure kneading zone 22 was maintained at 9.0 ± 1.5 MPa (first pressure). The decompression zone 23 was set to atmospheric pressure, and the first solvent and the second solvent were gasified and separated from the molten resin flowing into the decompression zone 23. The gasified first solvent and second solvent were sucked by the vacuum pump P, discharged from the vent 203 to the outside of the plasticizing cylinder 210, and collected in a collection container (not shown) connected to the vacuum pump P.

  By rotating the screw 20, the molten resin from which the first and second solvents have been separated is further flowed to the downstream replasticization zone 24, and then the string 29 is formed from the die 29 provided at the tip of the plasticizing cylinder 210. To obtain a first molded body containing nanoparticles.

  In this embodiment, the number of rotations of the plasticizing screw 20 was 100 rpm, and the amount of molten resin discharged from the die 29 was 2.5 kg / hr. Since the 1st solution whose PVP density | concentration in a solution is 46.3 g / L was supplied to molten resin at 12 mL / min, the supply amount of PVP with respect to molten resin is about 1.3 weight%. In addition, since the second solution having a concentration of 9.6 g / L of palladium complex with respect to liquid carbon dioxide was supplied to the molten resin at 8.7 mL / min, the supply amount of the palladium complex to the molten resin was about 2000 ppm by weight. The amount of metallic palladium supplied to the molten resin is about 400 ppm by weight. From the above, the ratio of metallic palladium to PVP is about 3% by weight.

(3) Manufacture of resin pellets The obtained string-like extrudate (first molded body) is passed through a water tank (not shown), and then continuously cut with a strand cutting device (not shown) to produce resin pellets. did.

(4) Evaluation of resin pellets The resin pellets produced in this example were visually observed. The resin pellets are blackened, and this is presumed to be due to the color of the palladium nanoparticles dispersed in the resin pellets. Further, visually, no aggregate was found in the resin pellet.

  The cross section of the pellet was observed with a TEM (transmission electron microscope). As shown in the TEM photograph of FIG. 6A, in the cross section of the resin pellet, a matrix in which a hydrophilic polymer domain (island) 2 exists in a matrix (sea) 1 made of the first thermoplastic resin- Domain structure (sea-island structure) was observed. And as shown in the TEM photograph of FIG.6 (b), several nanoparticle 3 was confirmed in the domain (island) 2 of a hydrophilic polymer. Most of the nanoparticles 3 existed in the domain (island) 2 of the hydrophilic polymer, and only a few nanoparticles 3 existed in the matrix (sea) 1 made of the first thermoplastic resin. . The nanoparticles 3 observed by TEM were isolated and dispersed without agglomeration. In addition to particles having a particle size of about several nanometers (10 nm or less) that can be confirmed in a TEM photograph, a hydrophilic polymer domain (island) 2 includes nanoparticles having a particle size of 1 nm or less, which is below the measurement limit of TEM. It was found from the contrast of the TEM photograph that there are many. From the structure of such resin pellets, nanoparticles are generated in the presence of a hydrophilic polymer. Therefore, it is presumed that the nanoparticles are agglomerated by suppressing aggregation.

  Next, the amount of palladium contained in the resin pellets was measured by ICP-MS (inductively coupled plasma mass spectrometer). As a result, the content of palladium in the resin pellet was 385 ppm by weight, and it was confirmed that almost the entire amount of palladium used as a raw material could be introduced into the resin pellet.

  In this example, the resin pellets were evaluated. However, since the resin pellets were obtained by cutting the first molded body, the first molded body can obtain the same evaluation results as the resin pellets. That is, the 1st molded object has the matrix-domain structure similar to a resin pellet in the inside, and the particle diameter and content of the nanoparticle to contain are the same as those of a resin pellet.

(5) Manufacture of 2nd molded object The 2nd molded object containing a nanoparticle was manufactured using the 2nd thermoplastic resin which does not contain a nanoparticle with the manufactured resin pellet. The resin pellets are mixed at a ratio of 10% by weight, ABS resin (second thermoplastic resin) 50% by weight, and ABS resin and PA alloy resin (second thermoplastic resin) 40% by weight. A 40 cm × 60 cm × 0.3 cm plate-shaped molded body (second molded body) was molded using an injection molding machine (manufactured by Nippon Steel Works, J180AD-300H). The molding temperature was 260 ° C. In this example, the alloy resin of ABS resin and polyamide (PA) used as the second resin contains 6 nylon components, thereby improving the wettability of the second molded body to the plating solution. .

(6) Electroless plating As a plating pretreatment, the second molded body was immersed in 2.5N hydrochloric acid at room temperature for 5 minutes, and then immersed in a 75 volume% aqueous solution of 1,3-butanediol at 70 ° C. for 10 minutes. Thereafter, the second molded body was immersed in an electroless nickel phosphorus plating solution (manufactured by Kanigen, SE-666) at 80 ° C. The plating reaction started 1 minute after immersion of the plating solution, and after 5 minutes, the electroless plating film was uniformly formed on the entire surface of the second molded body. Defects such as cracks and blisters did not occur in the plated film.

  In this example, although the ABS resin is used as the second thermoplastic resin, the nanoparticles (palladium particles) contained in the obtained molded body do not lose catalytic activity and are uniformly formed on the surface of the molded body. A successful plating film could be formed. This is presumably because the hydrophilic polymer covered the metal particles without being thermally decomposed, and the nanoparticles were protected from the volatile gas generated from the ABS resin during molding.

[Example 2]
In this example, in the production of the second molded body, 3% by weight of the resin pellets produced in Example 1, 50% by weight of the ABS resin (second thermoplastic resin), an alloy resin of ABS resin and PA (second product). The second molded body containing nanoparticles was produced by the same method as in Example 1 except that the mixture was mixed at a ratio of 47% by weight, and an electroless plated film was formed on the second molded body. did.

  In this example, the plating reaction was started 3 minutes after immersion of the second molded body in the plating solution, and after 15 minutes, the electroless plating film was uniformly formed on the entire surface of the second molded body. Defects such as cracks and blisters did not occur in the plated film.

[Comparative Example 1]
Instead of producing the first molded body by producing the nanoparticles in the molten resin, in this comparative example, the molding machine 4000 shown in FIG. 7 is used to produce the nanoparticles from the first solution and the second solution. The manufactured nanoparticles were mixed with the first thermoplastic resin, and a string-like first molded body was extruded. Other than that, using the same method as in Example 1, a resin pellet is manufactured, a second molded body is manufactured from the resin pellet and the second thermoplastic resin, and further, on the surface of the second molded body. A plating film was formed.

  In this comparative example, poly (2-vinylpyridine) (manufactured by Sigma-Aldrich, molecular weight 40000) is used as the hydrophilic polymer, ethanol is used as the first solvent, and a palladium complex is used as the metal salt. A second solution was prepared using hexafluoroacetylacetonato palladium (II) and n-hexane as the second solvent. A block copolymer having a hydrophilic segment (manufactured by Sanyo Chemical Industries, Pelestat 300) is used as the first thermoplastic resin for mixing the synthesized nanoparticles, and an ABS resin (manufactured by Toray Industries, Inc.) is used as the second thermoplastic resin. Toyolac 125X82) was used.

(1) Production of nanoparticles (a) Nanoparticle production apparatus The nanoparticle production apparatus 4000 used in this comparative example will be described. As shown in FIG. 7, the nanoparticle manufacturing apparatus 4000 includes a first solution supply mechanism 700, a second solution supply mechanism 800, a nanoparticle synthesis unit 900, and a nanoparticle recovery unit 950.

  The first and second solution supply mechanisms 700 and 800 are connected to the nanoparticle synthesis unit 900 via check valves 77 and 87, and supply the first solution and the second solution to the nanoparticle synthesis unit 900, respectively. To do. The first solution supply mechanism 700 includes a first solution supply container 70 in which a first solution is prepared, and the first solution is sucked from the first solution supply container 70, then the pressure is increased to a predetermined pressure, and the liquid is supplied at a constant flow rate. It consists of two possible syringe pumps 71 and 72, two suction air automatic valves 73 and 74 arranged in the pipe, and two liquid feed air automatic valves 75 and 76. The second solution supply mechanism 800 has the same configuration as that of the first solution supply mechanism 700, and the second solution supply container 80 in which the second solution is prepared, and after the second solution is sucked from the second solution supply container 80, It consists of two syringe pumps 81 and 82 that increase the pressure to a predetermined pressure, two suction air automatic valves 83 and 84 arranged in the pipe, and two liquid feed air automatic valves 85 and 86. Since the first and second solution supply mechanisms 700 and 800 have syringe pumps 71, 72, 81, and 82 capable of flow rate control and pressure control, the first and second solutions with the flow rate and pressure controlled to a predetermined amount are supplied. It can be sent to the nanoparticle synthesis unit 900. The syringe pumps 71, 72, 81, 82 open the suction air automatic valves 73, 74, 83, 84 to suck the solution into the syringe pump, then close the valves and pressurize them to maintain a predetermined pressure. . When liquid is fed, the liquid automatic air valves 75, 76, 85, and 86 are opened, and liquid can be fed at a constant flow rate by pushing the syringe of the syringe pump at a constant speed. The pressure at the time of flowing the pressurized fluid by the flow rate control is adjusted by the back pressure valve 99 at the end of the path. In each of the first and second solution supply mechanisms 700 and 800, when one pump (for example, syringe pumps 71 and 81) is feeding liquid, the other pump (syringe pumps 72 and 82) sucks and adds the solution. Press and wait. At the timing when the pressurized solution in one pump (syringe pumps 71, 81) that is feeding liquid becomes empty, the pump is switched, and this time, the other pump (syringe pumps 72, 82) feeds the liquid. Start. Accordingly, the first and second solutions can be supplied (supplied) from the first and second solution supply mechanisms 700 and 800 to the nanoparticle synthesis unit 900 with the pressure and the flow rate kept constant. The particle manufacturing apparatus 4000 can continuously manufacture nanoparticles. The second solution supply container 80 is a high-pressure sealed container so as to accommodate a high-pressure fluid such as pressurized carbon dioxide.

The nanoparticle synthesis unit 900 is connected to the first and second solution supply mechanisms 700 and 800 as described above, and is also connected to the nanoparticle recovery unit 950 via the pressure gauge 98 and the back pressure valve 99. The nanoparticle synthesis unit 900 prepares a mixed solution by mixing the first solution and the second solution supplied from the first and second solution supply mechanisms 700 and 800, and then synthesizes nanoparticles in the mixed solution. Then, the mixed solution containing the synthesized nanoparticles is sent to the nanoparticle recovery unit 950. The nanoparticle synthesis unit 900 includes a cylindrical electric furnace 90 having a pipe 91 spirally formed on the inner wall, and the inlet 90a side of the cylindrical electric furnace 90, that is, the first and second solution supply mechanisms 700 and 800. The cooling double pipe 92 arranged on the side, and the cooling double pipe 93 arranged on the outlet 90b side of the cylindrical electric furnace 90, that is, on the nanoparticle recovery unit 950 side. The first and second solutions supplied from the first and second solution supply mechanisms 700 and 800 are joined and mixed at the joining point 94 to form a mixed solution, and then the cooling double pipe 92 and the electric furnace 90 are provided. It flows through the spiral pipe 91 and the cooling double pipe 93 and is sent to the nanoparticle recovery unit 950. In the nanoparticle production apparatus 4000, a thickness of 0.5 mm (0.02) is provided in all pipes (tubes) through which the mixed solution including the pipe 91 in the electric furnace 90 and the double pipes 92 and 93 for cooling flow. Inch) and an outer diameter of 1.58 mm (1/16 inch) SUS316 piping. The length of the pipe 91 in the electric furnace 90 was about 2 m, and the internal volume of the pipe 91, that is, the volume of the nanoparticle synthesis reaction field was about 0.51 cm ³ .

  The nanoparticle recovery unit 950 includes a cyclone 95 that separates gas and liquid by centrifugation, and a recovery container 96 that recovers the solution from which the gas has been separated. When a high pressure vessel such as pressurized carbon dioxide is used as the second solvent, the second solvent is removed from the mixed solution by the cyclone 95. In this comparative example, since pressurized carbon dioxide was not used as the second solvent, the cyclone 95 was not used, and the mixed solution containing the synthesized nanoparticles was directly recovered in the recovery container 96.

(B) Production of Nanoparticles In the first solution supply container 70, poly (2-vinylpyridine), which is a hydrophilic polymer, was dissolved in ethanol, which is the first solvent, to prepare a first solution. The poly (2-vinylpyridine) concentration in the first solution was 3 g / L. In the 2nd solution supply container 80, the palladium complex was melt | dissolved as a precursor of a metal particle in n-hexane which is a 2nd solvent, and the 2nd solution was prepared. The palladium complex concentration in the second solution was 800 mg / L. At this time, the color of the second solution was yellow resulting from the palladium complex.

  Next, in the first solution supply mechanism 700, the suction air automatic valve 73 was opened, the first solution was sucked into the syringe pump 71, and the pressure was increased to 20 MPa. Similarly, in the second solution supply mechanism 800, the suction air automatic valve 83 was opened, the second solution was sucked into the syringe pump 81, and the pressure was increased to 20 MPa. At this time, the temperature in the syringe pumps 71 and 81 was normal temperature (25 ° C.).

  Next, the liquid automatic air valves 75 and 85 were opened, and both the first and second solutions were fed to the nanoparticle synthesis unit 900. The first and second solutions passed through check valves 77 and 87, merged at a junction 94, and mixed to form a mixed solution having a pressure of 10 MPa. The syringe pumps 71 and 81 are controlled so that the first solution and the second solution are mixed at a volume ratio of 1: 1, and further, the cooling double pipe 92, the pipe 91 in the electric furnace 90, and the cooling double pipe Through 93, the back pressure valve 99 was filled with a mixed solution having a pressure of 10 MPa. At this time, the temperature of the electric furnace 90 is controlled to 200 ° C., 20 ° C. cooling water is passed through the cooling double pipes 92 and 93, and the back pressure valve 99 displays the pressure gauge 98 as 10 MPa in advance. Controlled to be.

  Next, the syringe pumps 71 and 81 are switched to flow control, and a flow rate of 1 ml / min. The mixed solution was circulated in the pipe. One minute after starting the flow control of the syringe pumps 71 and 81, the mixed solution was dropped into the collection container 96 as a black liquid from the lower part of the cyclone 95. From the color of the collected mixed solution, it is presumed that the palladium complex of the raw material was decomposed and reduced to become palladium.

  Ethanol (first solvent) and n-hexane (second solvent) were removed from the mixed solution (black solution) collected in this comparative example by an evaporator to obtain a black powder.

(2) Evaluation of nanoparticle The obtained nanoparticle was thrown into ethanol and the dispersibility to ethanol was evaluated. The nanoparticles showed good dispersibility in ethanol without settling. From this result, it is surmised that the obtained nanoparticles were coated with a hydrophilic polymer.

  Next, the nanoparticles were observed by TEM. The particle diameter of the nanoparticles was about 3 to 5 nm, the primary particles were monodispersed without agglomeration, and the average particle diameter was about 4 nm. The average particle diameter of the nanoparticles is a value obtained by observing the nanoparticles with a TEM and measuring the particle diameters of 50 to 100 particles and averaging them.

(3) Manufacture of 1st molded object The synthesized nanoparticle was mixed with the 1st thermoplastic resin, and the 1st molded object containing a nanoparticle was manufactured. In this comparative example, using a general-purpose extruder (manufactured by Imoto Seisakusho Co., Ltd., single screw extruder), the nanoparticles and the block polymer are mixed and melted at 200 ° C. in the extruder, extruded, and stringed. A first molded body was obtained. In addition, the mixing ratio of the nanoparticles and the block polymer (first thermoplastic resin) was set so that the concentration of the nanoparticles in the resin pellet was 500 ppm.

(4) Production of resin pellets By the same method as in Example 1, the first molded body was cut to obtain resin pellets.

(5) Manufacture of 2nd molded object It mixes in the ratio of 10 weight% of manufactured resin pellets, and ABS resin (2nd thermoplastic resin) 90 weight%, and uses the same general purpose injection molding machine as Example 1. Thus, a similar plate-like second molded body was produced by the same method.

(6) Electroless plating An electroless plating film was formed on the manufactured second molded body by the same method as in Example 1. The plating reaction started 3 minutes after immersion of the plating solution, and after 10 minutes, an electroless plating film was uniformly formed on the entire surface of the second molded body. Defects such as cracks and blisters did not occur in the plated film.

  In this comparative example, although the ABS resin is used as the second thermoplastic resin, the nanoparticles (palladium particles) contained in the obtained molded body do not lose catalytic activity and are uniformly formed on the surface of the molded body. A successful plating film could be formed. This is presumed to be because the hydrophilic polymer covered the metal particles without being thermally decomposed, and the nanoparticles were protected from the volatile gas generated during molding from the ABS resin.

  However, the nanoparticles produced in Example 1 contain particles having a particle size of 1 nm or less, whereas the nanoparticles produced in this comparative example have a particle size of about 3 to 5 nm, which is compared with Example 1. It was big. For this reason, the activity as an electroless plating catalyst is slightly lowered as compared with Example 1, and therefore, it is presumed that the time required for electroless plating is increased as compared with Example 1.

[Comparative Example 2]
In this comparative example, except that the first solution containing the hydrophilic polymer and the first solvent was not used, the same material as in the example was used, and the first molded body was manufactured by the same method. The molded body was cut to produce resin pellets.

(1) Evaluation of resin pellet The resin pellet produced in this comparative example was observed visually. The resin pellets are blackened, and this is presumed to be due to the color of the palladium nanoparticles dispersed in the resin pellets. Further, visually, no aggregate was found in the resin pellet.

  The cross section of the pellet was observed with a TEM (transmission electron microscope). As shown in the TEM photograph of FIG. 8, nanoparticles 3 were confirmed in the first thermoplastic resin 1 in the cross section of the resin pellet. Nanoparticles observed by TEM had a particle size of 1 nm or less and were isolated and dispersed without agglomeration. In this comparative example, since no hydrophilic resin was used, there was no hydrophilic polymer domain (island).

  Next, the amount of palladium contained in the resin pellets was measured by ICP-MS (inductively coupled plasma mass spectrometer). As a result, the content of palladium in the resin pellet was 380 ppm by weight, and it was confirmed that almost the entire amount of palladium used as a raw material could be introduced into the resin pellet.

(2) Production of second molded body and electroless plating The same materials as in Examples were used except that the resin pellets produced in this comparative example were used instead of the resin pellets produced in Example 1. A second molded body was produced by the method described above. Further, the obtained second molded body was subjected to pre-plating treatment in the same manner as in Example 1, and the second molded body subjected to the pre-plating treatment was immersed in an electroless plating solution.

  However, the plating film did not grow on the second molded body produced in this comparative example. The reason is estimated as follows. In the manufacturing process of the second molded body, a volatile gas such as a styrene monomer was generated from the molten second resin and adsorbed on the palladium nanoparticles. And it is estimated that palladium was poisoned by the adsorption of volatile gas, and the electroless plating catalytic activity was deactivated.

  In Examples 1 and 2 described above, the first molding including nanoparticles using polyvinylpyrrolidone as the hydrophilic polymer, ethanol as the first solvent, liquid carbon dioxide as the second solvent, and palladium complex as the metal salt. Although the body was manufactured, this invention is not limited to this. For example, as the hydrophilic polymer, poly (2-vinylpyridine), poly (3-vinylpyridine), poly (4-vinylpyridine), polyvinylpyrrolidone, poly (N-vinylacetamide), poly (vinylamine) and polyvinyl alcohol And at least one selected from the group consisting of: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-1-propanol as the first solvent. At least one selected from the group can be used. Even if these materials are used, it is presumed that a product having the same characteristics as those of the first molded article, the resin pellet and the second molded article containing the nanoparticles obtained in Examples 1 and 2 can be produced.

  The nanoparticles contained in the molded article of the present invention have heat resistance that does not deactivate the catalytic activity even when brought into contact with a high-temperature molten resin, do not aggregate even at high temperatures, and have high dispersibility in the resin. . Therefore, in the molded body containing the nanoparticles of the present invention, the plating reactivity of the molded body is increased and the productivity is improved.

1 Matrix made of the first thermoplastic resin (sea)
2 Domain (island) of hydrophilic polymer
3 Nanoparticle 10 First solution storage container 30 Storage tank 11, 12, 31, 32 Syringe pump 13, 14, 33, 34 Automatic air valve for suction 15, 16, 35, 36 Automatic air valve for liquid feeding 20 Screw 21 Plastic Zoning zone 22 High pressure kneading zone 23 Depressurizing zone 24 Replasticizing zone S1 Upstream side sealing mechanism S2 Downstream side sealing mechanism 100 First solution supply mechanism 200 Extruder 210 Plasticizing cylinder 300 Second solution supply mechanism 1000 Production apparatus

Claims (29)

A method for producing a molded body, comprising:
Preparing a first solution comprising a hydrophilic polymer and a first solvent;
Preparing a second solution comprising a metal salt and a second solvent;
Plasticizing and melting the first thermoplastic resin to obtain a molten resin;
Generating nanoparticles from the metal salt in the molten resin by adding a first solution and a second solution to the molten resin;
The manufacturing method of the molded object characterized by including shape | molding the said molten resin containing the said nanoparticle in a desired shape.   The method for producing a molded body according to claim 1, wherein the hydrophilic polymer is a water-soluble polymer.   The hydrophilic polymer is composed of poly (2-vinylpyridine), poly (3-vinylpyridine), poly (4-vinylpyridine), polyvinylpyrrolidone, poly (N-vinylacetamide), poly (vinylamine), and polyvinyl alcohol. It is at least 1 type selected from a group, The manufacturing method of the molded object of Claim 1 or 2 characterized by the above-mentioned.   The method for producing a molded body according to any one of claims 1 to 3, wherein the first solvent is a polar solvent.   The method for producing a molded article according to claim 4, wherein the first solvent is alcohol.   6. The alcohol is at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-1-propanol. The manufacturing method of the molded object of description.   The method for producing a molded body according to any one of claims 1 to 6, wherein the second solvent is pressurized carbon dioxide.   The method for producing a molded body according to claim 7, wherein the pressurized carbon dioxide is liquid carbon dioxide.   The said metal salt is palladium salt, The manufacturing method of the molded object as described in any one of Claims 1-8 characterized by the above-mentioned.   The method for producing a molded body according to any one of claims 1 to 9, wherein the first thermoplastic resin is a block copolymer including a hydrophilic segment.   The method for producing a molded article according to claim 10, wherein the hydrophilic segment of the block copolymer is a polyether. A first solution and a second solution are continuously added to the molten resin to form a mixture,
The molded body according to any one of claims 1 to 11, wherein the pressure of the mixture is adjusted to a first pressure of 3 to 40 MPa while the first solution and the second solution are continuously added. Manufacturing method. And adjusting the pressure of the first solution and the second solution to a second pressure higher than the first pressure,
The method for producing a molded body according to claim 12, wherein the first solution and the second solution adjusted to the second pressure are added to the molten resin.   The molded body according to claim 12 or 13, further comprising adjusting the mixture to a pressure lower than the first pressure and separating the first solvent and the second solvent from the mixture. Production method. A method for producing resin pellets, comprising:
Manufacturing the first molded body by the method for manufacturing a molded body according to any one of claims 1 to 14,
Cutting the first molded body. A method for producing resin pellets, comprising: cutting the first molded body. A method for producing a molded body, comprising:
Producing resin pellets by the method for producing resin pellets according to claim 15;
The manufacturing method of the molded object characterized by including manufacturing the 2nd molded object containing the said nanoparticle using the said resin pellet and 2nd thermoplastic resin.   The method for producing a molded body according to claim 16, wherein the second thermoplastic resin is an ABS resin.   The method for producing a molded article according to claim 16 or 17, wherein the second thermoplastic resin does not contain the nanoparticles.   The method for producing a molded body according to any one of claims 16 to 18, wherein the second thermoplastic resin does not contain a block copolymer including a hydrophilic segment. A method for producing a molded body having a plating film,
Producing a second molded body by the method for producing a molded body according to any one of claims 16 to 19, and
A method for producing a molded body having a plating film, comprising forming an electroless plating film on a surface of the second molded body. A molded body,
A thermoplastic resin;
A hydrophilic polymer;
Contains nanoparticles,
The molded body has a matrix-domain structure in which a domain of the hydrophilic polymer containing the nanoparticles is present in a matrix made of the thermoplastic resin.   The molded article according to claim 21, wherein a particle diameter of the nanoparticles is 10 nm or less.   The molded body according to claim 21, wherein a particle diameter of the nanoparticles is 2 nm or less.   The said nanoparticle is a metal nanoparticle which functions as an electroless-plating catalyst, The molded object as described in any one of Claims 21-23 characterized by the above-mentioned.   The molded body according to claim 24, wherein the metal is palladium.   The hydrophilic polymer is composed of poly (2-vinylpyridine), poly (3-vinylpyridine), poly (4-vinylpyridine), polyvinylpyrrolidone, poly (N-vinylacetamide), poly (vinylamine), and polyvinyl alcohol. The molded article according to any one of claims 21 to 25, wherein the molded article is at least one selected from the group.   The molded article according to any one of claims 21 to 26, wherein the thermoplastic resin is a block copolymer including a hydrophilic segment.   The molded article according to any one of claims 21 to 27, wherein a ratio of the nanoparticles to the hydrophilic polymer is 0.1 to 30% by weight. Resin pellets,
A resin pellet produced by cutting the molded body according to any one of claims 21 to 28.

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